Public Abstract

DE-FG02-05ER15731: ATOMIC-SCALE DESIGN OF METAL AND ALLOY CATALYSTS: A COMBINED THEORETICAL AND EXPERIMENTAL APPROACH

Award Status: Active

Institution: Board of Regents of the University of Wisconsin System, operating as University of Wisconsin-Madison, Madison, WI
UEI: LCLSJAGTNZQ7
PM: Schwartz, Viviane

Most Recent Award Date: 09/03/2026
Number of Support Periods: 22
PI: Mavrikakis, Manos

Current Budget Period: 07/15/2026 - 07/14/2027
Current Project Period: 07/15/2026 - 07/14/2029

Public Abstract

Atomic-scale design of metal and alloy catalysts: A combined theoretical and experimental approach Dr. Manos Mavrikakis, Professor (lead-PI) Department of Chemical & Biological Engineering University of Wisconsin-Madison Madison, WI 53706 Catalysts are materials enabling chemical reactions to take place with significantly reduced energy requirements. Because chemical reactions consume a significant fraction of the annual energy production at the global scale, catalysts are essential for realizing significant energy savings. Our research aims to advance the understanding of transition metal-based catalytic systems under reaction conditions, with particular emphasis on the in-situ formation of sub-nanometric cluster sites and surface dynamics. Importantly, these dynamically formed cluster sites can be much more efficient catalysts than the most abundant catalytic sites on the same material. To obtain a precise, atomic-level description of catalytic reactions, a synergistic theory-experiment approach is required. State-of-the-art density functional theory (DFT) calculations combined with machine-learning interatomic potentials (MLIPs) and kinetic modelling approaches, such as mean-field microkinetic modelling (MF-MKM) and kinetic Monte Carlo (KMC) simulations, will enable the robust modelling of reaction kinetics under realistic reaction conditions. Experimentally, reactivity data will be obtained from reaction kinetics experiments, while advanced inorganic synthesis and in-situ characterization techniques will be used to probe catalyst structure and evolution. This integrated theory-experiment approach enables iterative validation and refinement of mechanistic models to achieve theory-experiment parity and provides key insights into the nature of the active sites dictating the overall catalytic performance. Beyond mechanistic insights, we aim to elucidate general reactivity trends and identify descriptors for catalytic activity, selectivity, and stability to guide the rational design and large-scale catalytic materials screening. Theory-driven predictions will be evaluated through advanced inorganic synthesis and in-situ characterization of shape-, size-, and composition-controlled nanocrystals, facilitating direct experimental validation of theoretical predictions. To achieve these goals, we will construct a comprehensive database for large-scale materials screening and identify catalysts susceptible to cluster formation under realistic reaction conditions. Promising candidate materials will be synthesized and investigated through the integration of DFT, MLIPs, MF-MKM, KMC, reaction kinetics experiments, and experimental characterization techniques to revisit the fundamental mechanism of relevant thermal catalytic and electrocatalytic reactions, such as the low temperature water-gas shift reaction (WGSR) and carbon dioxide electroreduction reaction (CO2RR). By elucidating how dynamic, reaction-driven restructuring of the catalyst influences catalytic performance (activity, selectivity, stability), this work will advance the foundational understanding of thermal and electrocatalytic processes and offer valuable insights into the evolution of catalyst structure under realistic reaction conditions. The resulting knowledge will yield new insights into the dynamic nature of the catalytically active sites and guide the rational design of improved catalysts, ultimately advancing the development of more efficient catalytic technologies that will lead to significant energy savings. The utility of this approach was demonstrated during the previous grant period, particularly in the following areas: (i) fundamental mechanistic studies elucidating the mechanism of reaction-driven formation of sub-nanometer clusters on transition metal catalysts; (ii) fundamental aspects of electrocatalysis, including operando observations of carbonyl-driven copper migration and adsorbate-induced cluster formation over Au-Cu alloys under CO2RR conditions; and (iii) development of novel methods for (a) theoretical modeling of reaction kinetics for thermal catalytic and electrocatalytic applications, including coverage-cognizant microkinetic models and machine-learned interatomic potentials, and (b) synthesis of high-loading single atom catalysts with improved electrocatalytic performance.

Atomic-scale design of metal and alloy catalysts: A combined theoretical and experimental approach

Dr. Manos Mavrikakis, Professor (lead-PI)

Department of Chemical & Biological Engineering

University of Wisconsin-Madison

Madison, WI 53706

Catalysts are materials enabling chemical reactions to take place with significantly reduced energy requirements. Because chemical reactions consume a significant fraction of the annual energy production at the global scale, catalysts are essential for realizing significant energy savings. Our research aims to advance the understanding of transition metal-based catalytic systems under reaction conditions, with particular emphasis on the in-situ formation of sub-nanometric cluster sites and surface dynamics. Importantly, these dynamically formed cluster sites can be much more efficient catalysts than the most abundant catalytic sites on the same material. To obtain a precise, atomic-level description of catalytic reactions, a synergistic theory-experiment approach is required. State-of-the-art density functional theory (DFT) calculations combined with machine-learning interatomic potentials (MLIPs) and kinetic modelling approaches, such as mean-field microkinetic modelling (MF-MKM) and kinetic Monte Carlo (KMC) simulations, will enable the robust modelling of reaction kinetics under realistic reaction conditions. Experimentally, reactivity data will be obtained from reaction kinetics experiments, while advanced inorganic synthesis and in-situ characterization techniques will be used to probe catalyst structure and evolution. This integrated theory-experiment approach enables iterative validation and refinement of mechanistic models to achieve theory-experiment parity and provides key insights into the nature of the active sites dictating the overall catalytic performance. Beyond mechanistic insights, we aim to elucidate general reactivity trends and identify descriptors for catalytic activity, selectivity, and stability to guide the rational design and large-scale catalytic materials screening. Theory-driven predictions will be evaluated through advanced inorganic synthesis and in-situ characterization of shape-, size-, and composition-controlled nanocrystals, facilitating direct experimental validation of theoretical predictions. To achieve these goals, we will construct a comprehensive database for large-scale materials screening and identify catalysts susceptible to cluster formation under realistic reaction conditions. Promising candidate materials will be synthesized and investigated through the integration of DFT, MLIPs, MF-MKM, KMC, reaction kinetics experiments, and experimental characterization techniques to revisit the fundamental mechanism of relevant thermal catalytic and electrocatalytic reactions, such as the low temperature water-gas shift reaction (WGSR) and carbon dioxide electroreduction reaction (CO2RR). By elucidating how dynamic, reaction-driven restructuring of the catalyst influences catalytic performance (activity, selectivity, stability), this work will advance the foundational understanding of thermal and electrocatalytic processes and offer valuable insights into the evolution of catalyst structure under realistic reaction conditions. The resulting knowledge will yield new insights into the dynamic nature of the catalytically active sites and guide the rational design of improved catalysts, ultimately advancing the development of more efficient catalytic technologies that will lead to significant energy savings.

The utility of this approach was demonstrated during the previous grant period, particularly in the following areas: (i) fundamental mechanistic studies elucidating the mechanism of reaction-driven formation of sub-nanometer clusters on transition metal catalysts; (ii) fundamental aspects of electrocatalysis, including operando observations of carbonyl-driven copper migration and adsorbate-induced cluster formation over Au-Cu alloys under CO2RR conditions; and (iii) development of novel methods for (a) theoretical modeling of reaction kinetics for thermal catalytic and electrocatalytic applications, including coverage-cognizant microkinetic models and machine-learned interatomic potentials, and (b) synthesis of high-loading single atom catalysts with improved electrocatalytic performance.